Light-sensitive materials

ABSTRACT

A light-sensitive material comprising a support having thereon a porous plastic layer, with a light-sensitive substance and a binder present in the pores of said layer, is disclosed.

United States Patent [191 Chiba et al.

[451 Dec. 18, 1973 LIGHT-SENSITIVE MATERIALS Inventors: Toshio Chiba; Teruhiko Yonezawa;

Jiro Kobayashi; Goro Akashi, all of Kanagawa, Japan Fuji Photo Film Co., Ltd., Kanagawa, Japan Filed: Nov. 25, 1970 Appl. No.: 92,878

Assignee:

Foreign Application Priority Data Nov. 26, 1969 Japan 44/94928 References Cited UNITED STATES PATENTS l/l955 Herrick et a1 96/49 X 2,893,867 7/1959 Dawson et al.' 117/34 X 2,939,009 5/1960 Tien 96/75 X 3,061,453 10/1962 Rogers 117/34 3,214,274 10/1965 Ohyama et aL... 117/34 X 3,272,629 9/1966 Hills 96/75 3,661,589 5/1972 Notley 117/34 X 3,235,381 2/1966 Feild, Jr. et a1 96/27 2,017,853 10/1935 Eichstadt 96/67 53,815 4/1866 Griswold... 96/67 705,643 7/1902 Buss 1. 96/67 3,216,882 11/1965 Feldt et al 161/109 2,305,169 12/1942 Lierg 96/75 X 3,264,134 8/1966 Vill et a1. 117/63 1,599,147 9/1926 Schmidt et a1 96/75 X 235,831 12/1880 Vogel 96/67 3,072,481 l/l963 Berman et a1. 96/48 3,421,932 l/l969 McGregor, Jr. et a1. 1 17/1053 Primary ExaminerCharles L. Bowers, Jr. Atz0rneySughrue, Rothwell, Mion, Zinn & Macpeak [5 7] ABSTRACT 'substance and a binder present in the pores of said layer, is disclosed.

9 Claims, No Drawings LIGHT-SENSITIVE MATERIALS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material. More particularly, the present invention relates to a light-sensitive material which is simple to make low in production costs and is high in resolving power, and which is abrasion-proof, water-proof, chemically resistant and weather-proof.

2. Description of the Prior Art In known light-sensitive materials, for example, print ing papers, the silver halide grains are dispersed in gelatine as a binder and coated onto a baryta paper. Lightsensitivc materials of this type intrinsically lack waterproof characteristics and the steps used in their production are complicated because gelatin is used as a binder.

It is a principal object of the invention to provide a new light-sensitive material in which the above mentioned disadvantages are overcome.

SUMMARY OF THE INVENTION The present invention comprises a light-sensitive material in which the production cost is low, in which the resolving power is excellent and which is water-proof, abrasion-proof, chemically resistant and weatherproof. The light-sensitive material is obtained by forming firstly a porous plastic layer and then forming or filling a light-sensitive substance such as silver halide in the pores of the plastic layer.

DETAILED DESCRIPTION OF THE INVENTION In the light-sensitive material of the invention, lightsensitive substances, such as light-sensitive silverhalides, diazo light-sensitive substances, ferrous ammonium citrate-red prussiate light-sensitive substances, organic halides such as carbon tetrabromide or its derivative, diphenylamine or its derivative light-sensitive substances, quinone diazide derivatives, leuco compunds-organic halogen generating agent lightsensitive substances, photochromic dyes, compounds which change color with pH and are capable of being transformed into an acid or base by radiation of light, and the like, are filled into plastic layers having a number of pores of from 0.1 to several microns in diameter. Where the light-sensitive substance is silver halide, for example, the silver grains are formed in the pores after exposure and development.

Therefore, the light-sensitive material of the invention is better from an abrasion-proof and water-proof standpoint in comparison with prior art light-sensitive materials. The abrasion-proof characteristics can further be raised, if desired, by treating the material with a solvent thus to close the pores.

As a method of forming a plastic layer having pores, the phase-separation process as shown in the following Examples as well as a known process employing the foaming action of foaming agents and high pressure gases as in the production of foamed styrols or ure thane foam rubbers can be used, but the former is more suitable for obtaining fine pores.

As a support member, any supporting material, such as paper, plastics, metals, glass and synthetic papers can be used.

Suitable silver halides which can be used are silver chloride, silver bromide, silver iodobromide and the like, depending on the end use. One feature of the invention is the formation of silver halide in the presence of the binder such as organic hydro colloid, for example, gelatin, gum arabic, polyvinyl alcohol, methyl cellulose, ethyl cellulose and the like in the pores of plastics. Moreover, it is easy to form a light-sensitive layer of so-called heat development type involving a developing agent capable of exhibiting a developing effect on heating, with formation of the silver halide in the pores of the plastics.

Another feature of the invention comprises treating the surface of the light-sensitive material with a solvent for the plastics, after development thereby closing the pores and resulting in stable water-proof, chemically resistant weather-proof developed image. As the solvent for this use, methylene chloride or ethyl acetate is suitable particularly in the TAC-DAC system of Example l, hereinafter set forth. Where vinyl chloride type resins are used as the plastic layer, a solvent such as methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and butyl acetate is suitable.

Plastic materials suitable for forming the pores are as follows:

Mixing Composition Ratio (Weight (Preferred range) weight) i. Triacety] cellulose (TAC)/ diacetyl cellulose (DAC) 95:5-5:95 :25-25:75 ii. TAC/nitrocellulose (NC) do. Do. iii. NC/DAC do. Do. iv. PVC-AC/PVC-AC1vinylchloride-vinyl acetate copolymers (PVC-AC) differing in mixing composition: 92:8-821l8 50:50-75:25 by weight] :10-10:90 75:25-25:75 v. TAC/cellulose propionate do. Do. vi. TAC/cellulose acetate Butyrate do. Do. vii. Styrol do. Do. viii. Polyurethane rubber do. Do. ix. Polyvinyl alcohol alone do. Do. x. PVC-AC alone (92:8-82:l8 or 50:50-75:25 by weight) do. Do.

The following examples are given to illustrate the invention in detail without limiting the same.

EXAMPLE 1 TAC and DAC in a weight ratio of 3:2 were dissolved in a mixed solvent of methylene chloride/methanol to give a concentration of 5 percent by weight. To the resulting solution was added water corresponding to 7 percent by weight of the solution and, directly before phase-separation, coated onto a water-proof paper of l 10 p. in thickness to give a thickness of 10p. on a dry basis followed by drying. The thus-obtained coating was a TAC-DAC layer having pores of about 0.3a.

Solution A: Aqueous Solution of 3 percent Silver Nitrate and 0.l percent gelatin Solution B: Aqueous Solution of 30 percent Potassium Bromide Solution C: Aqueous Solution of 20 percent Potassium Bromide and 2 percent Potassium Bichromate The above-described solutions were prepared and coated in the order of Solution A Solution B Solution C using a reverse roll type coating machine. During the coating, application of ultrasonic waves promoted the permeation of the solution in the pores. Silver bromide was formed in the form of fine grains in the pores of the foregoing porous plastic layer by the reaction of Solution A with Solutions B and C. A sheet having light sensitive characteristics was obtained.

EXAMPLE 2 The same procedure as described in Example 1 was repeated except that TAC and DAC in a weight ratio of 1:1 were dissolved in a mixed solvent of methylene chloride/methanol to give a concentration of 4.5 percent by weight. A light-scnsitive material was obtained.

EXAMPLE 3 NC and DAC in weight ratio of 1:1 were dissolved in a mixed solvent of methylene chloride/methanol/isopropanol to give a concentration of 3 percent by weight and mixed with vigorous agitation with water corresponding to 6.5 percent by weight of the total of the solution.

The resulting solution, directly before phaseseparation, was coated onto a vinyl chloride base having a coating of vinyl acetate to give a thickness of 8 p. on dry basis. The thus obtained NC-DAC layer had pores ranging from 0.6 to 1.8;}. as determined using an electron microscope of the scanning type.

Solution D: Aqueous Solution of 45 percent AgNO 0.8 percent Gum Arabic Solution E: Aqueous Solution of 2 percent KBr, 1

percent Kl Solution F: Aqueous Solution of 1 percent KBr, 0.5

percent K1, 1 percent Sodium Bichromate The above-described solutions were prepared and coated thereon in an order of D E F followed by drying. Silver halide was formed in the pores of the NC- DAC layer with a light-sensitive material being obtained.

EXAMPLE 4 To the porous plastic layer obtained by the method of Example 3 was applied a light-sensitive solution of the ferrous ammonium citrate-red prussiate type for blue print under action of ultrasonic waves and dried to obtain a light-sensitive material.

EXAMPLE 5 To the porous plastic layer obtained by the method of Example 3 were applied the following solutions in order and a light-sensitive material was obtained:

Amount i. Ethyl Cellulose 5 g Ethyl Alcohol 20 ml Toluene 20 ml Carbon Tetrabromide 2 g ii. 3-Benzylamino-7-dimethylaminofluoran 2 g Ethylene Dichloride ml As will be evident from the above-described examples, the light-sensitive material of the invention is a completely novel light'sensitve material.

What is claimed is:

l. A water-proof, abrasion-proof, weather-proof and chemically-resistant light-sensitive material having excellent resolving power consisting essentially of a support having coated thereon a fine porous plastic layer containing a light-sensitive substance and a binder therefor distributed in the fine pores of said layer, said fine pores having a diameter of from 0.1 to 1.8 microns, said porous plastic layer being formed by a process which consists essentially of:

dissolving at least two plastic materials which differ in their affinity for water in a solvent therefor to form a solution, said plastic materials are selected from the group consisting of triacetyl cellulose/diacetyl cellulose mixtures, triacetyl cellulose/nitrocellulose mixtures, nitrocellulose/diacetyl cellulose mixtures, vinyl chloride-vinyl acetate copolymer/vinyl chloride-vinyl acetate copolymer mixtures differing in the vinyl-chloride-vinyl acetate weight ratios, triacetyl cellulose/cellulose propionate mixtures and triacetyl cellulose/cellulose acetate butyrate mixtures,

adding water to said solution to form a mixture,

immediately before phase separation of the mixture,

coating said mixture onto said support,

drying the coated mixture to form said layer having said fine pores,

distributing said light-sensitive substance and said binder in the pores of said pore-containing layer, and

drying to form said light sensitive material.

2. A water-proof, abrasion-proof, weather-proof and chemically-resistant light-sensitive material having excellent resolving power consisting essentially of a support having coated thereon a fine porous plastic layer containing a non-silver salt light-sensitive substance and a binder therefor distributed in the fine pores of said layer, said fine pores having a diameter of from 0.1 to 1.8 microns, said porous plastic layer being formed by a process which consists essentially of:

dissolving at least two plastic materials which differ in their affinity for water in a solvent therefor to form a solution, said plastic materials are selected from the group consisting of triacetyl cellulose/diacetyl cellulose mixtures, triacetyl cellulose/nitrocellulose mixtures, nitrocellulose/diacetyl cellulose mixtures, vinyl chloride-vinyl acetate copolymer/vinyl chloride-vinyl acetate copolymer mixtures differing in the vinyl chloride-vinyl acetate weight ratios, triacetyl cellulose/cellulose proprionate mixtures and triacetyl cellulose/cellulose acetate butyrate mixtures,

adding water to said solution to form a mixture,

immediately before phase separation of the mixture,

coating said mixture onto said support,

drying the coated mixture to form said layer having said fine pores,

distributing said light-sensitive substance and said binder in the pores of said pore-containing layer, and

drying to form said light-sensitive material.

3. A water-proof, abrasion-proof, weather-proof and chemically-resistant light-sensitive material having excellent resolving power consisting essentially of a support having coated thereon a fine porous plastic layer consisting essentially of a light-sensitive substance and a binder therefor distributed throughout the fine pores of a plastic material selected from the group consisting of triacetyl cellulose/diacetyl/cellulose mixtures, triacetyl cellulose/nitrocellulose mixtures, nitrocellulose/- diacetyl cellulose mixtures, polyvinyl chloride/vinyl aeetate copolymer mixtures, triacetyl cellulose/cellulose propionate mixtures and triacetyl cellulose/cellulose acetate butyrate mixtures, the pores of said plastic layer having a diameter of from 0.3 to 1.8 microns, said porous plastic layer being formed by a process which consists essentially of:

dissolving said plastic material in a solvent therefor to form a solution, the components of the first three of the recited mixtures being present in weight ratios of from 95/5 to 5/95, the components of the last three mixtures being present in weight ratios of from 90/10 to l0/90,

adding water to said solution to form a mixture,

immediately before phase separation of the mixture,

coating said mixture onto said support,

drying the coated mixture to form said layer having said fine pores,

distributing said light-sensitive substance and said binder in the pores of said pore-containing layer, and

drying to form said light-sensitive material.

4. The light-sensitive material as claimed in claim 1, wherein the light-sensitive substance is selected from the group consisting of a light-sensitive silver halide, a diazo light-sensitive substance, at light-sensitive substance comprising an organic halide and diphenyl amine or its derivative, a quinone diazide derivative, a leuco compound organic halogen generating lightsensitive substance, a photochromic dye and a compound changing color with a pH change and capable of being transformed into an acid or base on radiation of light.

5. The light-sensitive material as claimed in claim 4, wherein the light-sensitive substance is selected from the group consisting of silver chloride, silver bromide, silver iodobromide and a mixture of carbon tetrabromide and a 3-benzylamino-7-diethylaminoflu0ran compound.

6. The light-sensitive material as claimed in claim 2, wherein the non-silver salt light-sensitive substance is a ferrous ammonium citrate-red prussiate compound.

7. The light-sensitive material as claimed in claim I wherein said fine pores have a diameter of 0.3 to 1.8 microns.

8. The light-sensitive material as claimed in claim 2 wherein said fine pores have a diameter of from 0.3 to 1.8 microns.

9. The light-sensitive material as claimed in claim 1,

wherein the binder is an organic hydrocolloid. 

2. A water-proof, abrasion-proof, weather-proof and chemically-resistant light-sensitive material having excellent resolving power consisting essentially of a support having coated thereon a fine porous plastic layer containing a non-silver salt light-sensitive substance and a binder therefor distributed in the fine pores of said layer, said fine pores having a diameter of from 0.1 to 1.8 microns, said porous plastic layer being formed by a process which consists essentially of: dissolving at least two plastic materials which differ in their affinity for water in a solvent therefor to form a solution, said plastic materials are selected from the group consisting of triacetyl cellulose/diacetyl cellulose mixtures, triacetyl cellulose/nitrocellulose mixtures, nitrocellulose/diacetyl cellulose mixtures, vinyl chloride-vinyl acetate copolymer/vinyl chloride-vinyl acetate copolymer mixtures differing in the vinyl chloride-vinyl acetate weight ratios, triacetyl cellulose/cellulose proprionate mixtures and triacetyl cellulose/cellulose acetate butyrate mixtures, adding water to said solution to form a mixture, immediately before phase separation of the mixture, coating said mixture onto said support, drying the coated mixture to form said layer having said fine pores, distributing said light-sensitive substance and said binder in the pores of said pore-containing layer, and drying to form said light-sensitive material.
 3. A water-proof, abrasion-proof, weather-proof and chemically-resistant light-sensitive material having excellent resolving power consisting essentially of a support having coated thereon a fine porous plastic layer consisting essentially of a light-sensitive substance and a binder therefor distributed throughout the fine pores of a plastic material selected from the group consisting of triacetyl cellulose/diacetyl/cellulose mixtures, triacetyl cellulose/nitrocellulose mixtures, nitrocellulose/diacetyl cellulose mixtures, polyvinyl chloride/vinyl acetate copolymer mixtures, triacetyl cellulose/cellulose propionate mixtures and triacetyl cellulose/cellulose acetate butyrate mixtures, the pores of said plastic layer having a diameter of from 0.3 to 1.8 microns, said porous plastic layer being formed by a process which consists essentially of: dissolving said plastic material in a solvent therefor to form a solution, the components of the first three of the recited mixtures being present in weight ratios of from 95/5 to 5/95, the components of the last three mixtures being present in weight ratios of from 90/10 to 10/90, adding water to said solution to form a mixture, immediately before phase separation of the mixture, coating said mixture onto said support, drying the coated mixture to form said layer having said fine pores, distributing said light-sensitive substance and said binder in the pores of said pore-containing layer, and drying to form said light-sensitive material.
 4. The light-sensitive material as claimed in claim 1, wherein the light-sensitive substance is selected from the group consisting of a light-sensitive silver halide, a diazo light-sensitive substance, a light-sensitive substance comprising an organic halide and diphenyl amine or its derivative, a quinone diazide derivative, a leuco compound organic halogen generating light-sensitive substance, a photochromic dye and a compound changing color with a pH change and capable of being transformed into an acid or base on radiation of light.
 5. The light-sensitive material as claimed in claim 4, wherein the light-sensitive substance is selected from the group consisting of silver chloride, silver bromide, silver iodobromide and a mixture of carbon tetrabromide and a 3-benzylamino-7-Diethylaminofluoran compound.
 6. The light-sensitive material as claimed in claim 2, wherein the non-silver salt light-sensitive substance is a ferrous ammonium citrate-red prussiate compound.
 7. The light-sensitive material as claimed in claim 1 wherein said fine pores have a diameter of 0.3 to 1.8 microns.
 8. The light-sensitive material as claimed in claim 2 wherein said fine pores have a diameter of from 0.3 to 1.8 microns.
 9. The light-sensitive material as claimed in claim 1, wherein the binder is an organic hydrocolloid. 